Asphaltic coating composition and materials coated therewith



I tioned application are improved by the addition Patented Nova 27, 1934 UNITED STATES PATENT ore-ice ASPHALTIC COATING COMPOSITION AND MATERIALS COATED 'nmanwrru Arthur N, Parrett, Milwaukee, Wis., assignor to E. I. du Pont de Nemours '8; Company, Wilmington, Del., a corporation of Delaware No Drawing. Application November 24, 1930, Serial No. 497,837

'1' Claim.

This invention relates to an improved asphalt varnish and to products coated therewith. More particularly this invention relates to artificial leather comprising fabrics or other flexible sheet material provided with a top coat of'the improved asphalt varnish. I i

For many years it has been customary to finish rubber coated fabrics for use as automobile top materials with a final coat of oil varnish, but all of such materialswith which I am familiar have rapidly deteriorated and quickly lost their gloss on exposure to the direct rays of the summer sun,

of improved asphalt varnishes.

A further object resides in the production ,of an improved artificial leather or coated fabric, which is especially adapted for use as an automobile top material. Other objects will appear hereinafter.

I have discovered thatthe coated products of the character referred to in the previously menor organic iron compounds. My improved varnish, which is of special utility as a top coating for rubber coated fabrics such as used for automobile top material, may be made by dissolving the asphalt in a suitable solvent with the aid of heat and-stirring, and adding to the asphalt solu tion the organic iron compound dissolved in an appropriate solvent. Better results are obtained, however, by the incorporation of bodied or raw drying oils into the composition, and to this end the iron compound is added to the asphalt solution with the oil dissolved in asuitable solvent or thinner, such as turpentine. As an alternative imethod, however, the iron compound. may be cooked into the oil prior to blending the oil with the asphaltic constituent of the varnish. This method is best suited to diflicultly soluble iron salts, such as basic ferric acetate.

With the above and other objects in view, which will be apparent as the-description proceeds, .I have set forth my invention inthe following specification and have included the following examplesv by way of illustration and not as a limitation.

Example 1 Parts by weight Petroleum residue asphalt 100 Solvent naphtha 100 Turpentine 20 Bodied China wood oil 17.59 Iron resinate 2.41

The asphalt is heated to 500 F., allowed to cool to 425 R, an equal weight of solvent naphtha is added, and the mixture is stirred until the asphalt is completely dissolved. To this solution is, added 40 parts by weight of a turpentine solution of 'China wood oil bodied with iron resinate.

The oil used in the above varnish is prepared from the following ingredients, using the proportions indicated:

Parts by weight Raw China wood oil 87.95 Iron resinate containing 7.3% iron 12.05

' 100.00 The China wood oil is heated to 385 F., and the iron resinate is' added at this temperature, slowly and with constant stirring. The oil is then heated up to 425 F. in one hour and maintained at this temperature for 30 minutes,

Examplez Parts by weight Petroleum residue asphalt 100 Solvent naphtha 100 Turpentine 40 Bodied China wood oil 35.55 Iron oleate 4.45

The asphalt is heated to 500 F., allowed to cool Example4 Parts by weight Petroleum residue asphalt; 100 Solvent naphtha 1 00 Turpentine 80 Bodied China wood oil 10.96 Iron'linoleatem 9.04

to 425 F., an equal weight of solvent naphtha is added, and the "mixture is stirred until the asphalt is completely dissolved. To this solution is added 80 parts by weight of a 50% turpentine solution of China wood oil bodied with iron oleate.

The oil used in the above varnish is prepared from the following ingredients, using the proportions indicated:

. Parts by weight Raw China Wood oil 88.86 Iron oleate containing 8% iron 11.14

TheChina wood oil is heated to 385 F., and the iron oleate is added'slowly at this temperature. The oil is then heated to 425 F. in the course of one hour-and kept at this temperature for 30 The asphalt is heated to 500 F., allowed to cool to 425 F., anequal weight of solvent naphtha is added, and the mixture is'stirred until the asphalt is completely dissolved. To this solution is added 120 parts by weight of a 50% turpentine solution of China .wood oil bodied with iron laurate (the iron salt. of coconut oil acids). j

The oil used in the above varnish is prepared from the following-ingredients, using the proportions indicated:

Parts by weight Raw China wood oil 91.95 Iron laurate containing 11.43% iron 8.05

The China wood oil is heated to 385 F., and the iron laurate is added slowly and with constant stirring. The oil is then heated to 425 F. in the course of one hour and kept at this temperature for 30 minutes. l

The asphalt is heated to 500 F., allowed to cool to 425 F., an equal weight-of solvent naphtha is.

Y added, and the mixture is stirred until the asphalt is completely dissolved. To this solution is added 160 parts by weight of a 50% turpentine solution of China wood oil bodied with iron linoleate.

The oil used in the above varnish is prepared from the following ingredients, using the proportions indicated:

, The asphalt is heated to 500 F., allowed to Y Parts by Y r weight Raw China wood oil 84.03

Iron linoleate containing 5.3% iron 15.97

g 100.00 The China wood oil is-heated to 385 F., and the iron linoleate is added slowly and with constant stirring. The oil is then heated to 425 F. in one hour and kept at this temperature for 30 minutes.

Example 5 Parts by I weight Petroleum residue asphalt i 100 Solvent naphtha 100 Turpentine 120 Bodied China wood oil 106.63 Iron naphthenate 13.87

cool to 425 F., an equal weight of solvent naphthais added, and the mixture is stirred until the asphalt is completely dissolved. To this solution is added 240 parts by weight of a 50% turpentine solution of China wood oil bodied with iron naphthenate.

'The oil used in the above varnish is prepared from the following ingredients, using the proportions indicated: g Parts by weight Raw china wood oil 88. 86 Iron naphthenate containing 8% iron..-" 11. 14

The China wood oil is heated to 385 F., and the iron naphthenate. is added slowly and with constant stirring at this temperature. The oil is then heated to 425 F., in the course of one hour and kept at this temperature for 30 minutes.

Example 6 q Parts by weight Petroleum residue asphalt 100' Solvent naphtha 100 Turpentine 160 Bodied linseed oil 140. 72 Iron resinate 19.28

Theasphalt is heated to 500 F., allowed to cool to 425 F., an equal weight of solvent naphtha is added, and the mixture is stirred until the asphalt.

is completely dissolved. To this solution is added 320 parts by weight of a 50% turpentine solution .of linseed oil bodied with iron resinate.

The oil used in the above varnish is prepared from the following ingredients, using the proportions indicated:

Parts by weight Lin'seedoil 87. Iron resinate containing 7.3% iron 12.05

The oil is heated to 450 F. and the iron reslnate is added slowly and with constant stirring. The oil is then heated to 600 F. in the course of one hour and maintained-at this temperature for 45 minutes.

Example 7 Parts by weight Petroleum residue asphalt 100 Solvent naphtha 100 Turpentine 344 Linseed oil 320 Iron oleate s 40 iron.

Example 8 Parts by a weight Petroleum residue asphalt 100 Solvent naphtha 100 Turpentine 120 Bodied China wood oil 105. 54 Iron resinate 14. 4'6

The asphalt is heated to 500 F., allowed to cool to 425 R, an equal weight of solvent naphtha is added, and the mixture is stirred until theasphalt is completely dissolved. To this solution is added 640 parts by weight of a 50% solution of linseed oil in turpentine and 64 parts by weight of a turpentine solution of iron oleate containing 5% The asphalt is heated to 500 F., allowed to cool to 425 F., an equal weight of solvent naphtha is added, and the mixture is stirred until the asphalt is completely dissolved. To this solution is added 240 parts by weight of a 50% turpentine solution of the Chinawood oil bodied with iron resinate, the preparation of which is described in Example 2.

Example 9 Parts by weight Gilsonite 100 Solvent naphtha 100 Turpentine 160 Bodied China wood oil 140. '72 Iron resinate 19. 28

The gilsonite is heated to 500 -F., allowed to cool to 425 R, an equal amount'of solvent naphtha is added, and the mixture is stirred until the gilsonite is completely dissolved.\ To this solution is added 320 parts by weight of a. 50% turpentine solution of China wood oil bodied with iron resinate, the preparation of which is described in Example 2.

Example 10 Parts by weight Gilsonite- 100 Solvent naphtha 100 Turpentine 258 Linseed oil 240 Iron oleate i 30 The gilsonite is heated to 500 F., allowed tocool to 425 F., an equal weight of solvent naphtha is added, and the mixture is stirred until the gilsonite is completely dissolved; To this solution is added 480 parts by weight of a 50% solution of raw linseed oil in turpentine and 48 parts by weight of a solution oi. iron oleate containing 5% iron.

Example 11 Parts by weight Petroleum residue asphalt 100 Solvent naphtha 100 Turpentine 45. 48 Raw China wood oil 40 Iron resinate 5.48

The asphalt is heated to 500 F., allowed to cool to 425 F., an equal weight of solvent naphtha is added, and the mixture is stirred until the asphalt is completely dissolved. To this solution is added parts by weight of a 50% solution of raw China wood oil in turpentine and 10.96 parts by weight of a 50 turpentine solution of iron resinate con-' tainin 3.66% iron.

I Example 12 Parts by weight Petroleum residue asphalt 100 Solvent naphtha L. 100 Turpentine 80 Linseed oil 80 Iron ricinoleate 20 The asphalt is heated to 500 F., allowed to cool to 425 F., an equal weight of solvent naphtha is added, and the mixture is stirred until the asphalt is completely dissolved. To this solution is added 160 parts by weight of a 50% solution of raw linseed oil in turpentine and 20 parts by weight of a 50% turpentine solution of iron ricinoleate con- The asphalt is heated to 500 F, allowed to cool to 425 R, an equal weight of solvent naphtha is added, and the mixture is stirred until the asphalt is completely dissolved. To this solution is added 240 parts by weight of a 50% solution of raw linseed oil in solvent naphtha and 88.8 parts by weight of a 29.6% toluol solution of ferric butyl phthalate containing 1.35% iron.

Example 14 Parts by weight Petroleum residue asphalt 100 Solvent naphtha 100 Turpentine 40 Bodied China wood oil 36.07 Iron tungate 3.93

The asphalt is heated to 500 F., allowed to cool to 425 R, an equal weight of solvent naphtha is added, and the mixture is stirred until the asphalt is completely dissolved. To this solution is added parts by weight of a 50% turpentine solution of China wood oil bodied with iron tungate (the iron salt of China woodoil acids).

The oil used in the above varnish is prepared from the following ingredients, using the proportions indicated:

P s y weight Raw China wood oil 90.1.! Iron tungate containing 9.18 iron 9.83

The China wood oil is heated to 385 F. and the iron tungate is added at this temperature, slowly and with constant stirring. The oil is then heated to 425 F. in one hour and maintained at this temperature for 30 minutes.

The iron tungate referred to above may be de-' fined as a compound prepared by reacting ferrous or ferric salts of iron with tung oil acids or their salts.

The varnishes set forth above, as well as other varnishes falling within the scope of the present invention, are highly useful in finishing rubbercoated fabrics, and particularly those to be used as automobile top materials. In the manufacture of such materials the varnish may be applied either as 'a single coat directly over the rubber coated fabric, or it may be applied as the final coat in a two coat system in which the intermediate coat is preferably a long oil varnish. However, other intermediate varnishes, such as suitable asphalt varnishes, have been used with excellent results.

An example of an oil varnish suitable as an intermediate coating between the rubber and asphalt coatings is as follows:

In the one-coat system, which is the simplest form of my invention, the coat of asphalt varnish is applied over the uncured rubber and .then subjected to heating at a suitable temperature and for a sufiicient time to vulcanize the rubber and to thoroughly fuse the asphalt film. By this treatment I obtain on the surface of the goods a smooth, continuous film which is substantially inert and which remains for a long time unaffected by sunlight. The temperature and time of cure depend on the rubber compound, and especially on the kind and quantity of vulcanizing agent used. As a rule, the temperature will lie between 240 to 275 F., and the time of cure'will be from 30 minutes to 3 hours.

When using my two-coat system, I first apply over the uncured rubber an intermediate coat of varnish-such as an oil varnish. This coat may phalt varnish and. finish by baking at a temperature of about 240 to 275 F. for such time as is required to complete the vulcanization of the rubber;

In some cases it is advantageous, after applying the intermediate varnish coat, to bake at the vulcanizing temperature for a portion of the .vulcanizing period and to complete the vulcanization of the rubber by baking at the same temperature after the final coat of asphalt varnish has been applied. This procedure somewhat shortens the total time required to complete the process, but it is important that care should be taken on the one hand to avoid overvulcanization of the rubber, and on the other hand that the final coat should receive not less than about one hours treatment at the full vulcanizing temperature in order to produce the best results and to properly condition-the asphalt varnish film. However, I do not wish to limit my invention to a process which involves baking the final asphalt coat of a two-coat system, since good results may be obtained with a two-coat system of which the first coat is a baked oil varnish and the second coat an air-dried asphalt varnish.

The two-coat system is preferred to the onecoat system, especially over a rubber coated fabric, because it has greater flexibility and retains its gloss for a longer time. Without limiting myself thereto, I believe this is due to the elastic from petroleum residue asphalt which has been refined by other.methods, as for instance, by

- coat of intermediate varnish acting as a buffer blowing with air. The characteristics desired in the asphalt depend somewhat, however, on the manner in which the varnish is to be applied and dried. When the varnish is to be baked at the in ordereto obtain with this type of asphalt the maximum durability and retention of luster on exposure to the weather. For varnishes which are to be air-dried or baked at lower temperatures, as temperatures lower than required for vulcanization of the rubber, harder asphalts should be used, the preferred being petroleum residue asphalts prepared by team refining processes which melt about 200 F., as determined by the ball and ring method previously referred to. Among other asphalts especially suitable for varnishes to be air-dried or baked at .low temperatures may be mentioned Gilsonites and other natural bitumens.

Other suitable drying oils, such as perilla or soya bean oil, may be used instead of thosementioned in the examples. In general, raw or bodied oils may be employed, but when China wood oil is employed in other than very short gallon lengths, care must be taken to cure or body it sufiiciently to prevent wrinkling, as is well known in l50 the varnish art. The purpose in using the drying oil'is to decrease the brittleness of the asphalt when it is spread in a thin film. From 2 to 7 gallons of oil to lbs. of asphalt is generally sufficient for this purpose, but in some cases where a high degree of elasticity is desired I may use with good results as high as 15- or even 30 gallons of oil per 100 lbs. of asphalt. .My preferred compositions, however, contain less Oil than asphalt. Pigments, fillers, or toughening agents, such as carbon black may be ground with the oil before mixing with the asphalt where it is desired to toughen the film or to obtain additional protection against sunlight. The term gallon is used herein'in accordance with the general usage in the varnish trade as designating a weight of 8 pounds of oil per 100 pounds of gum, the gum in the present instance being asphalt. For example a five gallon asphalt-oil varnish contains approximately forty parts by weight of oil to one hundred pounds of asphalt.

The iron compounds may be dissolved in suitable thinners or solvents or they may be cooked into the oil prior to blending the oil with the asphalt. While a wide variety of iron organic compounds may be employed, I prefer to use the iron salts, either ferrous or ferris, of such acids as abietic acid, oleic acid, linseedoil acids, China wood oil acids, and similar compounds because these materials are easily prepared either by pre: cipitating or fusion processes.

Whereas I have specified the addition of iron organic compounds, it will be apparent that the iron organic compounds may also be formed in situ by cooking some iron inorganic compounds with the constituents of the varnish.

While I prefer to use enough iron compound so that the system contains about 1% iron, based on the oil content of the varnish, good results are obtained if this amount is varied, for example between 0.5% and 4.0%. However, quantities larger than 1.0% are not especially advantageous except in dimcultly compatible systems.

While driers are sometimes desirable in my improved asphalt coatings containing drying oils, it is to he understood that the invention resides, not in the use of these iron compounds as driers. but in the discovery that the iron compounds inpart improved properties to the asphalt ,coatings especially with respect to longer retention of the luster of the'finish. In my preferred composition containing drying oils these improved properties are due chiefly to my discovery that the incorporation of the organic iron compounds causes superior blending of homogeneous system, as compared to the blending effect produced by other metallic compounds which function as driers. It will be seen, therefore, that with respect to the main object of the invention, the drying function of the iron compounds is incidental, because the drying function, if absent from the particular organic iron compound used, could be supplied bythe addition of any of the known driers other than an iron compound. is evidenced by the large quantity of drying oil that may be incorporated into the asphaltdrying oil varnish when the organic iron compounds are used, as compared to the quantity that may be incorporated when other metallic driers are used.

Forty-gallon asphalt-bodied China wood oil (320 lbs. oil per 100 lbs,,aspha1t) varnishes have been prepared with the iron compounds herein disclosed whereas satisfactory varnishes exceeding 25 gallons in oil length (200 lbs.- ofl per 100 lbs.

the asphalt and oil into a.

The blending power of iron compounds.

asphalt)--cannot be made with other metal driers.

Exposure tests of material finished with asphalt-oil varnishes containing organic salts of iron and similar asphalt varnishes containing metallic driers other than from salts; show conclusively the beneficial effects of the iron compound by the better retention of luster and the lesser tendency of the coating to check and to show separation of the components of the coating. The superior luster retaining properties of my improved coated materials appears also to be due partly to the power of the iron compounds to retard or absorb the ultraviolet rays present in sunlight and thereby shield the coating from their destructive effect. In this connection attention is directed 'to the fact that varnishes containing no oil, as the varnish of Example 1, yield coatings of longer retention of luster than a similar varnish in which the iron compound is replaced by salts of metals other than iron.

Various other solvents, such as mineral spirits, benzene, and toluene, may be used for dissolving the asphalt, as will be understood by those skilled in the art. The solvent selected should prefer ably be one in which the organic iron compound is soluble, and these compounds are soluble in the usual asphalt solvents such as those mentioned above. Since the organic iron compounds are very easily soluble in turpentine, it is preferred first to dissolve the iron compound in turpentine and then to add this solution to the asphalt solution. "3

It will, therefore, be apparent that I have developed new and useful coated fabrics which possess improved capability of retaining a high luster over a long period of time as compared with materials heretofore available, and new and useful processes for producing same. While said processes and coated fabrics have been described in connection with rubber coated fabrics, since ments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to, the specific embodiments thereof except as defined in the appended claims.

I claim: a

- 1. A process for making artificial leather which comprises applying over a rubber coated fabric sheeting a varnish coating comprising drying oil,

asphalt, a solvent for the asphalt, an organic iron compound soluble in said solvent, and baking the resulting product, the organic iron compound being present in suchan amount to increase the compatibility of the asphalt with the oil so that 100 pounds of the asphalt may be mixed in homogeneous blend with at least 320 pounds of the oil.

2. As an article of manufacture a rubber coated flexible fabric sheeting having a final coat of dried varnish comprising drying oil asphalt and an organic iron compound soluble in organic var 3 m'sh solvents, the organic iron compound being present in such an amount to increase the compatibility of the asphalt with the oil so that 100 pounds of the asphalt may be mixed in homo geneous blend with at least 320 pounds of the oil.

3. The process set forth in claim 1 in which said organic iron compound is present in the varnish in an amount equal to from 0.5% to 4% iron based upon the weight of the drying oil present in the varnish.

4. The process set forth in claim 1 in which said organic iron compound is present in an amount equal to about 1% iron based upon the weight of the drying oil present in the varnish.

5. The process set forth in claim 1 in which said organic iron compound is a salt of an acid selected from the class consisting of fatty acids, abietic acid, naphthenic acid, and half acid esters of polybasic acids.

6. The article set forth in claim 2 in which said organic iron compound is a salt of. an acid selected from the class consisting of fatty acids, abietic acid, naphthenic acid, and half acid esters of polybasic acids. 7

'1. The article set forth in claim 2 in which the organiciron compound is present in the final coat of dried varnish in an amount equal to from 0.5% to 4% iron based upon the weight of the drying oil present.

ARTHUR N. PARRE'I'I. 

